JP2010118321A - Active material for secondary battery, and secondary battery - Google Patents

Abstract

（式（Ｃ）及び／又は（Ｄ）中、ｍ、ｐは１〜１０の整数、ｎは正の整数であり、ｎの値はそれぞれ独立して選択可能である。）
【選択図】なしThe present invention provides a secondary battery having high current charge / discharge characteristics and high energy density.
By using a polymer compound represented by formula (C) or (D) as a positive electrode active material for a battery, a secondary battery having excellent large current charge / discharge characteristics and high energy density can be obtained.

(In formulas (C) and / or (D), m and p are integers of 1 to 10, n is a positive integer, and the values of n can be independently selected.)
[Selection figure] None

Description

  The present invention relates to an active material for a secondary battery that can realize a secondary battery that is excellent in large current charge / discharge characteristics and has a high energy density, and a secondary battery using the same.

  With the widespread use of electronic devices such as notebook computers, mobile phones, and digital cameras, the demand for secondary batteries for driving these electronic devices is increasing. In recent years, the power consumption of these electronic devices has increased with the progress of higher functionality, and the reduction in size is expected. Therefore, an increase in capacity is required for secondary batteries. Among secondary batteries, lithium ion secondary batteries are used in various electronic devices because of their high capacity.

  However, since a general lithium ion secondary battery uses a lithium-containing transition metal oxide having a large specific gravity for the positive electrode, it cannot be said that the secondary battery capacity per unit mass is sufficient, and a lighter electrode material can be used. Attempts to develop high-capacity secondary batteries using the same have been studied.

  For example, Patent Document 1 discloses a secondary battery using a conductive polymer as a positive electrode or negative electrode material. This is a secondary battery based on the principle of doping and dedoping of electrolyte ions accompanying redox of a conductive polymer.

  Since the conductive polymer is composed only of elements having a low specific gravity such as carbon and nitrogen, it is expected that the secondary battery capacity per unit mass will be increased. However, the doping of the electrolyte ions caused by the oxidation or reduction reaction of the conductive polymer is delocalized over a wide range of the π-electron conjugated system and has the property that they interact with each other. Limit battery capacity. Therefore, a secondary battery using a conductive polymer as an electrode material has a certain effect in terms of weight reduction, but is insufficient in terms of a large capacity.

  On the other hand, Patent Document 2 discloses a secondary battery using a radical compound as a substance involved in the electrode reaction. This is a battery based on the principle of doping and dedoping reactions of electrolyte ions accompanying redox of stable radicals.

Radical compounds are also composed only of elements with a low specific gravity such as carbon and nitrogen. Furthermore, in radical compounds, unpaired electrons that react are localized in radical atoms, increasing the concentration of reactive sites. Therefore, a high capacity secondary battery can be expected. Moreover, in this oxidation-reduction process, the oxidation-reduction reaction rate is large because there is no change in the chemical bonding state in the molecule and the ion diffusion process in the solid like the lithium-containing transition metal oxide that is the positive electrode material of the lithium battery, Charging / discharging with a large current is possible.
U.S. Pat. No. 4,442,187 Japanese Patent No. 3687736

  The present invention has been completed in view of the above circumstances, and provides an active material for a secondary battery capable of realizing a secondary battery having excellent high-current charge / discharge characteristics and high energy density, and a secondary battery using the same. Is a problem to be solved.

  As a result of intensive studies aimed at solving the above-mentioned problems, the present inventors have represented an organic compound that has not been used as an active material for a secondary battery until now, represented by the following general formula (A) or (B). It has been found that the compound can be used as an active material for a secondary battery. By adopting this active material for a secondary battery, a secondary battery having excellent large current charge / discharge characteristics and high energy density could be realized.

  (1) The active material for a secondary battery of the present invention is characterized by having (i) a polymer compound represented by the following general formula (A) or (B), or (ii) ) A monomer mixture mainly composed of a unit compound represented by the following general formula (E) and / or (F) was polymerized by elimination of hydrogen bonded to other than R1 to R4 of the unit compound. It has a high molecular compound. Furthermore, (iii) it has the high molecular compound which is a copolymer which has general formula (A) and / or (B) as a partial structure, It is characterized by the above-mentioned.

(In the formulas (A) and (B), R1 to R4 are independently selected from hydrogen and an alkyl group having 1 to 4 carbon atoms, and at least one of R1 to R4 is represented by the following general formulas (1) to (1) (It is one of the structures represented by (3). N is a positive integer, and the values of n can be selected independently.)

(In formulas (E) and (F), R1 to R4 are each independently selected from hydrogen and an alkyl group having 1 to 4 carbon atoms, and at least one of R1 to R4 is represented by the following general formulas (1) to (1) (It is one of the structures represented by (3).)

(Formulas (1) to (3) are bonded to the carbon atom of the benzene ring in the formulas (A), (B), (E) and (F) at the part *. Formulas (1) to (3 ), R is H, OH, CH ₃ or NH _{2. In} formulas (1) to (3), Y is — (CH ₂ ) _m — (m is an integer of 0 to 10), and m is When it is 1 or more, one or more methylene groups constituting Y are —O—, —NH—, —CH═N—, —S—, —CO—,

で置換されてもよい。）

May be substituted. )

  The specifically desirable polymer compound is a compound represented by the following formula (C) and / or (D). A compound having a structure represented by the following formula (C) and / or (D) as a partial structure may be used. Moreover, the compound which is a copolymer which has a structure represented by the following Formula (C) and / or (D) as a partial structure may be sufficient. In the case of a copolymer, any copolymer such as a random copolymer or a block copolymer may be used.

（式（Ｃ）及び／又は（Ｄ）中、ｍ、ｐは１〜１０の整数、ｎは正の整数であり、ｎの値はそれぞれ独立して選択可能である。）

(In formulas (C) and / or (D), m and p are integers of 1 to 10, n is a positive integer, and the values of n can be independently selected.)

  The monomer mixture in the active material for a secondary battery according to (ii) is pyrrole, pyrrole in which one or more hydrogen atoms are substituted with an alkyl group having 1 to 4 carbon atoms, thiophene, one or more hydrogens. The thing containing the thiophene by which the atom was substituted by the C1-C4 alkyl group is also employable.

  These heterocyclic aromatic compounds can be copolymerized with the unit compound represented by the general formula (E) and / or (F) to form a conductive polymer compound. Therefore, there is a possibility that high conductivity can be realized by adjusting the addition amount and the type of the heterocyclic aromatic compound to be added, and the addition amount and type can be selected and adjusted so as to obtain the required performance. The heterocyclic aromatic compound can be copolymerized with the unit compound represented by the general formula (E) and / or (F) by elimination of hydrogen, and the general formula (E) and / or (F). Those capable of forming a conjugated system by copolymerization with a unit compound represented by

  (2) The secondary battery of the present invention is a battery that employs the active material for a secondary battery described in (1) as an active material for a positive electrode and / or a negative electrode. In particular, it is desirable to employ the positive electrode active material. Further, it may be adopted as a positive electrode active material and mixed with a lithium-containing transition metal oxide.

  The active material for a secondary battery of the present invention is a polymer compound having a radical site in the side chain, and has a polyphenylene structure and / or a polyphenyleneethynylene structure in the main chain.

  The polymer compound is composed of only elements having a small specific gravity such as carbon and nitrogen, and further, unreacted unpaired electrons are localized in the radical atom, so that the concentration of the reaction site can be increased. Therefore, a high capacity secondary battery can be expected. Moreover, in this oxidation-reduction process, the oxidation-reduction reaction rate is large because there is no change in the chemical bonding state in the molecule and the ion diffusion process in the solid like the lithium-containing transition metal oxide that is the positive electrode material of the lithium battery, Since charging / discharging with a large current can be realized, a secondary battery having excellent large current charging / discharging characteristics and high energy density can be realized by employing this active material for a secondary battery.

(Active material for secondary battery)
The active material for a secondary battery of the present embodiment includes (i) a polymer compound represented by the general formula (A) and / or (B), or (ii) the general formula (E) and / or ( The monomer mixture containing the unit compound represented by F) as a main component has a polymer compound polymerized by elimination of hydrogen bonded to other than R1 to R4 of the unit compound. The molecular weight of the polymer compound is not particularly limited. For example, a molecular weight that dissolves in the electrolyte and does not dissipate into the electrolyte in the battery can be employed, or a molecular weight that becomes a solid can be employed. Specifically, a value having a molecular weight of about 1000 to 100,000 can be adopted. Therefore, the value of n in each formula is determined according to the molecular weight.

  The polymerization reaction performed for the purpose of obtaining the polymer compound (ii) is not particularly limited. A polymer compound that is soluble in any organic solvent can also be produced by general chemical polymerization. If a polymer compound soluble in an organic solvent is produced, an electrode can be formed by applying and drying the solution. Further, even if the polymer compound is insoluble in a solvent, the polymerized polymer compound can be attached to the surface of the current collector. For example, electrolytic polymerization can be exemplified.

  Furthermore, in addition to the unit compound of the general formula (E) and / or (F), other monomers can be copolymerized. Although it does not specifically limit as another monomer which can be copolymerized, it has a structure which can fully exhibit electroconductivity (for example, pyrrole, one or more hydrogen atoms are C1-C4 alkyl groups) Substituted pyrrole, thiophene, and thiophene in which one or more hydrogen atoms are substituted with an alkyl group having 1 to 4 carbon atoms can be employed. By copolymerizing other monomers, it is possible to control the affinity and stability to the electrolytic solution.

  When a compound having a structure that can sufficiently exhibit electrical conductivity as described above is used as a monomer, a mixture of the unit compound of general formula (E) and / or (F) and other monomers May be present as a main component in the monomer mixture. The mixing ratio of the unit compound of the general formula (E) and / or (F) and the other monomer is not particularly limited, but a range of about 1:10 to 10: 1 can be adopted. In particular, it is desirable to contain 1/2 or more unit compounds of the general formula (E) and / or (F).

  The general formula (A) is a polymer compound having a polyphenylene structure in which the benzene ring is polymerized in the main chain, and the general formula (B) is a polymer having a polyphenylene ethynylene structure formed by bonding of phenylene ethynylene in the main chain. A compound. General formulas (E) and (F) are derivatives in which one or more of the hydrogen atoms in the benzene ring are substituted, and are compounds that polymerize when hydrogen bonded to other than R1 to R4 is eliminated. R1 to R4 are each independently selected from hydrogen and an alkyl group having 1 to 4 carbon atoms, and at least one of R1 to R4 is any one of the structures represented by the general formulas (1) to (3). It has.

  The structures represented by the general formulas (1) to (3) have a stable radical structure. The stable radical structure is bonded to the main chain composed of a polyphenylene structure and / or a polyphenyleneethynylene structure via the Y structure. As the properties required for the structure represented by Y, it is required to secure a space that allows counter-counter ions to enter and exit the polymer compound (the interval between adjacent main chains is about 10 mm). Furthermore, it is also required that the stable radical structure be separated to such an extent that it does not inhibit the polymerization reaction that creates a main chain having a polyphenylene structure and / or a polyphenyleneethynylene structure.

  Y basically has a structure in which 0 to 10 methylene groups are bonded. Here, when the methylene group is 0, it means that it is bonded to the Y portion without anything. Y represents an arbitrary methylene group such as —O—, —NH—, —CH═N—, —S—, —CO—,

で置換されてもよい。

May be substituted.

  Desirable polymer compounds include compounds having the following structure and compounds represented by the above formulas (C) and / or (D) (m is 0 to 10), and particularly the above formula (C) and A compound represented by (D) (m, p is 0) is desirable. In addition, n in the following chemical formula is a positive integer and can be independently selected. The molecular weight is determined according to the value of n.

(Secondary battery)
The secondary battery of the present embodiment has a configuration in which the above-described secondary battery active material of the present embodiment is employed as at least one of a positive electrode active material and a negative electrode active material. Specifically, an electrode can be manufactured by forming a film containing a polymer compound as a main component on a current collector made of some conductive material. A general method can be adopted as a method of forming the film.

When the secondary battery active material of this embodiment is employed for one electrode, it is desirable to employ it as a positive electrode active material. In that case, as the negative electrode active material, lithium, a lithium alloy, or a material capable of occluding and releasing lithium is used. Examples of the material capable of occluding and releasing lithium include carbon materials such as graphite, coke, and fired organic polymer compound. A metal oxide such as a lithium-containing transition metal oxide can be further mixed with the positive electrode active material. Examples of the metal oxide include LiCoO ₂ , LiNiO ₂ and LiMn ₂ O ₄ .

  The secondary battery of this embodiment is composed of a known material such as a positive and negative electrode, a separator that electrically insulates between both electrodes, a current collector that collects current from an electrode active material, an electrolytic solution, and a battery case. .

The electrolyte is a medium that transports charge carriers such as ions between the positive electrode and the negative electrode, and is not particularly limited, but is physically, chemically, and electrically stable in the atmosphere in which the secondary battery is used. desirable. For example, examples of the non-aqueous electrolyte include LiBF ₄ , LiPF ₆ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) (C ₄ An electrolytic solution in which one or more selected from F ₉ SO ₂ ) is used as a supporting electrolyte and dissolved in an organic solvent is preferable. Examples of the organic solvent include propylene carbonate, ethylene carbonate, 1,2-dimethoxyethane, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran and the like and mixtures thereof. Among them, an electrolytic solution containing a carbonate solvent is preferable because of its high stability at high temperatures. A solid polymer electrolyte containing the above electrolyte in a solid polymer such as polyethylene oxide can also be used.

  Hereinafter, each example will be shown to describe the present invention in more detail, but the present invention is not limited thereto.

(Synthesis Example 1: Compound of formula (C), m, p = 0)
Synthesis of 2,5-diiodo-1,4-benzenedicarboxylic acid and 4-hydroxy-2,2,6,6, -tetramethylpiperidine-1-oxyl diester (Compound A) In a 300 mL Schlenk tube under nitrogen atmosphere 2,2,6,6-tetramethylpiperidine-4-hydroxy-N-1-oxyl (1.74 g), triethylamine (10 mL), toluene (100 mL) were added. A toluene (50 mL) solution of 2,5-diiodo-1,4-dibenzenecarboxylic acid chloride (2.30 g) was added dropwise over 1 hour, and the reaction solution was stirred at room temperature for 21 hours. The reaction solution was added to water and extracted with chloroform. The organic layer was washed with saturated brine, and then dried using sodium sulfate. Next, filtration is performed, and the filtrate is concentrated, and then purified by alumina column chromatography (developing solvent: chloroform) to obtain the following formula:

で表される化合物Ａを２．８２ｇ得た。

As a result, 2.82 g of the compound A represented by the formula:

The spin concentration of compound A thus obtained was measured with an electron spin resonance apparatus. The measurement device was JEOL-JES-FE2XG, and measurement was performed under the conditions of a microwave output of 8 mW, a modulation frequency of 100 kHz, and a measurement range of 335.0 mT ± 10 mT. As a result of measuring the spin concentration in comparison with the absorption area intensity of a known sample measured under the same conditions as the absorption area intensity obtained in the above measurement, the spin concentration of Compound A was 1.0 × 10 ²¹ spin / g or more. It was confirmed that a radical was formed.
UV-visible absorption spectrum (nm): 323 (chloroform solution)
Infrared spectrum (cm ⁻¹ ): 3437, 3082, 2974, 2934, 2867, 1715, 1462, 1366, 1331, 1279, 1261, 1224, 1179, 1140, 1125, 1046, 962, 938, 908, 838, 777 688, 563, 481

(Synthesis Example 2: Synthesis of compound of formula (C), m, p = 0)
Under a nitrogen atmosphere, a 100 mL Schlenk tube was charged with bis (1,5-cyclooctadiene) nickel (0) (0.83 g), 2,2′-bipyridyl (0.47 g), dehydrated N, N— Dimethylformamide (25 mL) and 1,5-cyclooctadiene (0.32 mL) were added. Compound A (0.73 g) was added over 1 hour and the reaction solution was stirred at 80 ° C. for 48 hours. The reaction solution was poured into a mixed solvent of methanol and water to reprecipitate the polymer compound. The obtained precipitate was washed twice with methanol and water and twice with methanol, and then dried under reduced pressure to obtain 0.26 g of a polymer.

で表される高分子化合物Ａの構造をもつものと推察される。 From the starting material, the polymer has the following formula:

It is guessed that it has the structure of the high molecular compound A represented by these.

Further, the spin concentration of the obtained polymer was measured with an electron spin resonance apparatus. The measurement device was JEOL-JES-FE2XG, and measurement was performed under the conditions of a microwave output of 8 mW, a modulation frequency of 100 kHz, and a measurement range of 335.0 mT ± 10 mT. As a result of measuring the spin concentration in comparison with the absorption area intensity of the known sample measured under the same conditions as the absorption area intensity obtained in the above measurement, the polymer spin concentration is about 1.0 × 10 ¹² spin / g. It was confirmed that a radical was formed. The spin concentration of the polymer is lower than that of Compound A, and some of the —NO · radical groups may react with the nickel complex and be converted to other groups.
Infrared spectra ^(cm -1): 3437,2974,2937,2812,1715,1634,1463,1383,1315,1285,1238,1176,1118,1068,996,961,833,756,640,444

(Synthesis Example 3: Synthesis of diester (compound B) of 2,5-diethynyl-1,4-benzenedicarboxylic acid and 4-hydroxy-2,2,6,6, -tetramethylpiperidine-1-oxyl)
To a 100 mL Schlenk tube purged with nitrogen, compound A (0.73 g), tetrakis (triphenylphosphine) palladium (0) (0.12 g), copper (I) iodide (0.02 g), triethylamine (10 mL), dehydrated toluene (20 mL), and dehydrated tetrahydrofuran (30 mL) were added and heated to 50 ° C. to dissolve. Trimethylsilylacetylene (0.34 mL) was added and the reaction solution was stirred at 50 ° C. for 18 hours. The reaction solution was added to saturated brine, the organic layer was collected, and the aqueous layer was extracted with chloroform. The collected organic layer was dried over sodium sulfate, filtered through celite, and purified by alumina column chromatography (developing solvent: chloroform). After transferring to a 100 mL eggplant-shaped flask and distilling off the solvent, it was dissolved in tetrahydrofuran (15 mL). A tetrahydrofuran solution (0.7 mL) of 1M tetra-n-butylammonium fluoride was slowly added dropwise and stirred at room temperature for 1 hour. The reaction solution was added to saturated brine and extracted with chloroform. The collected organic layer was dried over sodium sulfate and purified by alumina column chromatography (developing solvent: chloroform). By washing the obtained solid with methanol, the following formula:

で表される化合物Ｂを２３６ ｍｇ得た。

236 mg of the compound B represented by the formula:

The spin concentration of compound B thus obtained was measured with an electron spin resonance apparatus. The measurement device was JEOL-JES-FE2XG, and measurement was performed under the conditions of a microwave output of 8 mW, a modulation frequency of 100 kHz, and a measurement range of 335.0 mT ± 10 mT. As a result of measuring the spin concentration in comparison with the absorption area intensity of a known sample measured under the same conditions as the absorption area intensity obtained by the above measurement, the spin concentration of Compound B was 1.0 × 10 ²¹ spin / g or more. It was confirmed that a radical was formed.
UV-visible absorption spectrum (nm): 327 (chloroform solution)
Infrared spectrum (cm ⁻¹ ): 3441, 3262, 3210, 2974, 2936, 2869, 2104, 1720, 1631, 1463, 1436, 1393, 1376, 1365, 1311, 1287, 1232, 1180, 1113, 1022, 1003 , 916, 839, 787, 694

Synthesis Example 4: Synthesis of Compound of Formula (D), m, p = 0
In a 50 mL Schlenk tube purged with nitrogen, compound A (0.22 g), compound B (0.16 g), tetrakistriphenylphosphine palladium (0) (0.04 g), copper (I) iodide (0. 006 g), dehydrated N, N-dimethylformamide (10 mL), and triethylamine (5 mL) were added. The reaction solution was stirred at 50 ° C. for 48 hours. The reaction solution was reprecipitated by pouring into methanol, and the resulting solid was washed with water, dissolved in chloroform, and reprecipitated with methanol. The solid was filtered off and dried under reduced pressure to obtain a polymer (0.26 g).

Further, the spin concentration of the obtained polymer was measured with an electron spin resonance apparatus. The measurement device was JEOL-JES-FE2XG, and measurement was performed under the conditions of a microwave output of 8 mW, a modulation frequency of 100 kHz, and a measurement range of 335.0 mT ± 10 mT. As a result of measuring the spin concentration in comparison with the absorption area intensity of the known sample measured under the same conditions as the absorption area intensity obtained in the above measurement, the polymer spin concentration was 1.0 × 10 ²¹ spin / g or more. It was confirmed that a radical was formed.

で表される高分子化合物Ｂの構造をもつものと推察される。 From the starting material, the polymer has the following formula:

It is guessed that it has the structure of the high molecular compound B represented by these.

UV-visible absorption spectrum (nm): 396 (chloroform solution), 419 (film)
Infrared spectrum (cm ⁻¹ ): 3444, 3052, 2974, 2938, 2869, 2204, 1727, 1634, 1500, 1464, 1435, 1412, 1377, 1364, 1286, 1230, 1179, 1110, 1026, 1002, 979 963, 935, 786, 746, 694

[Example 1]
(Preparation of positive electrode)
Normal methylpyrrolidone (NMP) was added to 30 parts by mass of the polymer compound A, 60 parts by mass of carbon black, and 10 parts by mass of polyvinylidene fluoride (PVDF), and mixed and dispersed to prepare a homogeneous coating liquid. This homogeneous coating liquid was applied to one side of an aluminum current collector (film thickness 50 μm), dried, pressed, and then cut into a predetermined size to produce a positive electrode. The thickness of the produced positive electrode was 100 μm including the aluminum current collector.

(Preparation of negative electrode)
A negative electrode was prepared by cutting lithium metal foil (300 μm) into a predetermined size.

(Preparation of electrolyte)
Ethylene carbonate and ethyl methyl carbonate were mixed at a volume ratio of 3: 7, and LiPF ₆ was dissolved in the mixed organic solvent as a supporting electrolyte at a concentration of 1 mol / L to obtain an electrolytic solution.

(Production of battery)
A flat plate-shaped electrode body was formed by sandwiching a polypropylene separator between the positive electrode and the negative electrode obtained above. The obtained flat electrode body was inserted into the case and held in the case. Then, after inject | pouring the said electrolyte solution in the case holding the flat electrode body, the case was sealed and sealed. Through the above procedure, a coin-type battery having a diameter of 19 mm and a thickness of 3 mm was manufactured and used as a test battery of this example.

(Battery evaluation)
The prepared battery was charged from 2.5 V to 4.1 V at a current value of 0.1 mA, and then discharged from 4.1 V to 2.5 V at a current value of 0.1 mA. A discharge curve was shown, and the capacity per battery active material was 53 mAh / g.

  Next, after charging from 2.5 V to 4.1 V again at a current value of 0.1 mA, discharging from 4.1 V to 2.5 V at a current value of 1.0 mA, the capacity per electrode active material is The discharge capacity was 48 mAh / g, and a discharge capacity of about 90% during discharge was obtained at 0.1 mA.

[Example 2]
An electrode and a battery were prepared and evaluated in the same manner as in Example 1 except that the polymer compound B was used instead of the polymer compound A. As a result, a flat discharge curve was shown at around 3.5 V, and the battery capacity at the time of 0.1 mA discharge was 101 mAh / g.

  Moreover, the battery capacity at the time of 1.0 mA discharge was 93 mAh / g, and about 92% of the discharge capacity at the time of discharge was obtained at 0.1 mA.

[Comparative Example 1]
An electrode and a battery were produced and evaluated in the same manner as in Example 1 except that LiNiO ₂ was used instead of the polymer compound A. As a result, the battery capacity at the time of 0.1 mA discharge was 138 mAh / g.

  The battery capacity at 1.0 mA discharge was 78 mAh / g, and a discharge capacity of about 56% at the time of discharge was obtained at 0.1 mA.

[Comparative Example 2]
An electrode and a battery were prepared and evaluated in the same manner as in Example 1 except that carbon black was used instead of the polymer compound A. As a result, a flat discharge curve was not seen, and almost no battery capacity was obtained.

(result)
Therefore, it was found that a battery produced using the polymer compounds A and B of the present invention for the positive electrode has higher performance than a battery employing a conventional active material or the like for the positive electrode.

It is a longitudinal cross-sectional view which shows roughly an example of the structure of the coin-type battery of the nonaqueous electrolyte secondary battery of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Positive electrode 1a ... Positive electrode electrical power collector 2 ... Negative electrode (metallic lithium foil)
DESCRIPTION OF SYMBOLS 3 ... Electrolyte solution 4 ... Positive electrode case 5 ... Negative electrode case 6 ... Gasket 7 ... Separator 10 ... Coin type nonaqueous electrolyte secondary battery

Claims (7)

An active material of the positive electrode and / or the negative electrode in a secondary battery having a positive electrode, a negative electrode, and an electrolyte, and having a polymer compound represented by the following general formulas (A) to (B) Active material for secondary batteries.

(In the formulas (A) to (B), R1 to R4 are independently selected from hydrogen and an alkyl group having 1 to 4 carbon atoms, and at least one of R1 to R4 is represented by the following general formulas (1) to (1) (It is one of the structures represented by (3). N is a positive integer, and the values of n can be selected independently.)

(Formulas (1) to (3) are bonded to the carbon atom of the benzene ring in the formulas (A) to (B) at the part *. In formulas (1) to (3), R is H, OH. CH ₃ or NH _{2. In the} formulas (1) to (3), Y is — (CH ₂ ) _m — (m is an integer of 0 to 10), and when m is 1 or more, Y is constituted. One or more methylene groups are -O-, -NH-, -CH = N-, -S-, -CO-,

May be substituted. ) The active material for a secondary battery according to claim 1, wherein the polymer compound is represented by the following formula (C) and / or (D).

(In formulas (C) and / or (D), m and p are each independently selected from integers of 1 to 10. n is a positive integer, and the values of n can be independently selected. .) An active material for the positive electrode and / or the negative electrode in a secondary battery having a positive electrode, a negative electrode, and an electrolyte, the unit material being a unit compound represented by the following general formula (E) and / or (F) An active material for a secondary battery, comprising a polymer compound polymerized by elimination of hydrogen bonded to a unit mixture other than R1 to R4 of the unit compound.

(In formulas (E) and (F), R1 to R4 are each independently selected from hydrogen and an alkyl group having 1 to 4 carbon atoms, and at least one of R1 to R4 is represented by the following general formulas (1) to (1) (It is one of the structures represented by (3).)

(Formulas (1) to (3) are bonded to the carbon atom of the benzene ring in formulas (E) and (F) at the part *. In formulas (1) to (3), R is H, OH. CH ₃ or NH _{2. In the} formulas (1) to (3), Y is — (CH ₂ ) _m — (m is an integer of 0 to 10), and when m is 1 or more, Y is constituted. One or more methylene groups are -O-, -NH-, -CH = N-, -S-, -CO-,

May be substituted. )   The monomer mixture is pyrrole, pyrrole in which one or more hydrogen atoms are substituted with an alkyl group having 1 to 4 carbon atoms, thiophene and / or one or more hydrogen atoms are substituted with alkyl groups having 1 to 4 carbon atoms. The active material for secondary batteries of Claim 3 containing the made thiophene.   It is a positive electrode active material, The active material for secondary batteries of any one of Claims 1-4.   The active material for secondary batteries of Claim 5 which has a lithium containing transition metal oxide.   It is a secondary battery which has a positive electrode, a negative electrode, and electrolyte, Comprising: The active material of this positive electrode and / or this negative electrode is the active material for secondary batteries in any one of Claims 1-6 characterized by the above-mentioned. Secondary battery.

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